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Upon photoirradiation, isomerization of the ligands, 1,2-bis(diphenylphosphino)ethene (dppee) from the cis to the trans form in polynuclear gold(I) sulfido clusters, led to the structural transformation of the decagold(I) cluster to the octadecagold(I) cluster. Both polynuclear μ3-sulfido gold(I) clusters have been fully characterized by NMR, mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. The transformation process could be readily detected and monitored by UV-vis absorption, emission, and (31)P NMR spectroscopy in solution. Supported and driven by Au(I)···Au(I) bonding interactions, the nuclearity and symmetry of these clusters were largely different from each other, resulting in completely distinct photophysical features.

Photoinduced Isomerization-Driven Structural Transformation Between Decanuclear and Octadecanuclear Gold(I) Sulfido Clusters